Photographic coating formulation

ABSTRACT

Novel amphoteric surfactants having the formulas: WHEREIN R is an aliphatic hydrocarbon radical having from eight to 20 carbon atoms, R&#39;&#39; is selected from the group consisting of hydrogen, and alkyl radicals having from one to four carbon atoms, X is an integer of one-five and M is hydrogen, ammonium, nitrogen containing bases such as diethanolamine, triethanolamine, triethylamine, morpholine and piperidine, an alkali metal, and are used as wetting agents in gelatin coating compositions and photographic gelatin silver halide emulsions.     D R A W I N G

United States Patent [72] Inventors E. ScudderMackey Bingharnton, N.Y.;Fred S. Eiseman, Maplewood, NJ. [21] AppLNo. 772,388 [22] FiledOct.31,l968 [45] Patented Nov. 9, 1971 [73] Assignee GAF Corporation NewYork, N.Y.

[54] PHOTOGRAPHIC COATING FORMULATION 7 Claims, No Drawings [52] U.S.Cl96/l14.5, 96/94, 106/1 3 [51] 1nt.CL G03c 1/38 [50] FieldofSearch 96/84,114.5, 94; 106/125 [56] References Cited UNITED STATES PATENTS 2,271,6232/1942 Carroll 96/104 2,468,012 4/1949 lsbell .260/501.11X 3,017,2711/1962 Piper 96/107 3,113,026 12/1963 Sprung... 96/107 3,133,816 5/1964Ben-Ezra.... 96/85X 3,441,413 4/1969 Nishioetal.... 96/1l4.5 1,915,3346/1933 Salzbergetal. 260/243 2,075,359 3/1937 Salzbergetal 424/250Primary Examiner-William D. Martin Assistant Examiner-M. R. LusignanAttorneys-George L. Tone, Samson B. Leavitt and Walter C.

Kehm

ABSTRACT: Novel amphoteric surfactants having the formulas:

CH,CH;( %I- X(CH,)xcH sO M CHgCH C-N(CH;)1CH SO M wherein R is analiphatic hydrocarbon radical having from eight to 20 carbon atoms, R isselected from the group consisting of hydrogen, and alkyl radicalshaving from one to four carbon atoms, X is an integer of one-five and Mis hydrogen, ammonium, nitrogen containing bases such as diethanolamine,triethanolamine, triethylamine, morpholine and piperidine, an alkalimetal,and are used as wetting agents in gelatin coating compositions andphotographic gelatin silver halide emulsions.

PHOTOGRAPIIIC COATING FORMULATION This invention relates to photography,and more particularly, to a new class of coating aids or wetting agentsuseful in coating and washing photographic material such as film orpaper.

The use of wetting agents in the coating of photographic materials iswell known. A number of such wetting agents have been recommended andused in conjunction with emulsions, dye washes, rinses, noncurling (NC)layers and antihalation layers. These wetting agents include saponinwhich is derived from vegetable sources and a considerable number ofsynthetic surfactants of the anionic, cationic and nonionic type. Theseknown surfactants have been found not to be entirely satisfactorybecause of the formation of repellency spots, mottle, streakiness and/orair bells in the coating. Especially harmful is the formation of airbells which are not present in the original film but appear only duringor after development.

Therefore, it is an object of this invention to provide a surfactant foruse in photography that is free of the drawbacks of the prior artwetting agents.

A further object of this invention is to provide a wetting agent for usein photography which has superior coating qualities and does not produceair bells in the coating.

Still another object of the instant invention is to provide a coatingagent for use in photography which has antistatic properties.

Other objects will be apparent from the following description.

The objects and advantages of this invention are accomplished byincorporating in a photographic coating composition an amphotericsurfactant which is a ,B-alanine derivative and characterized by one ofthe following formulas;

FORMULA 1 In these formulas, R represents an aliphatic hydrocarbon chainof from eight to 20 carbon atoms such as octyl, nonyl, decyl, undeeyl,dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl andoctadecyl; R representshydrogen or an alkyl radical containing from oneto four carbon atoms such as methyl, ethyl, propyl or butyl; x is aninteger of from one to five and M represents hydrogen, ammonium,nitrogen containing bases such as diethanolamine, triethanolamine,triethylamine, morpholine or piperidine, an alkali metal.

These compounds have the additional advantage of permitting "wet-on-wet"coatings which means that they have the ability to facilitate thespreading of a colloidal layer over a previously coated emulsion layerwhich is chilled, but still wet, thus eliminating an additional coatingpass and an extra drying operation.

The coating compositions in which the novel surfactant may beincorporated may be any of the coating compositions used in thephotographic art; for example, those used for the preparation ofphotographic emulsions, gelatin surface coatings, NC layers, dye washes.rinses, antihalation layers, dyes and antistatic layers.

The wetting agents of this invention may be used in amounts ranging from0.02 to 0.5 percent by volume based on the total volume of the coatingsolution. Based on the amounts of gelatin used, the alanine derivativesused in accordance with my invention are added to the liquidphotographic emulsions or other aqueous gelatin dispersions or solutionsin proportions ranging from 1-40 grams per kilogram of dry gelatinemulsion. Expressed in terms of coated areas, the effective amountsrange from 0.1 to 5 milligrams per square foot of coated area.

The process used in coating the solutions containing the novel wettingagent of this invention may be any one of the known processes used inthis art; such as, air knife, applicator pan, extrusion or dip pancoating. In the coating operations with the surfactants of thisinvention, both paper and film supports may be utilized. Suitable filmsupports include cellulose esters such as cellulose acetate, cellulosepropionate, cellulose acetate-butyrate; vinyl esters such as thecopolymers of vinyl acetate and vinyl chloride, polystyrene,polycarbonate and the polymers derived from terephthalates.

The B-alanines derivatives of my invention, when used alone, havesatisfactory photographic properties; they do not cause fog or loss ofspeed and prevent the formation of air bells. These wetting agents areespecially useful in permitting coating operations at very high speeds.

The novel wetting agents of this invention may be used as a coating aid,either alone or in conjunction with any known surfactant or wettingagent; such as, the taurides, protein condensation products of fattyacids, saponin or polyoxyethylene derivatives of long-chain fatty acidsand alcohols.

We have found that compounds of the above type may be produced by thereaction of a primary amine having the requisite number of carbon atoms,with an ester of acrylic acid such as methyl acrylate. As disclosed inU.S. Pat. No. 2,468,0l2 the amino propionate ester thus produced may behydrolyzed to the free acid or may be converted to any of the saltsmentioned above.

The condensation between the amine and the acrylic ester proceedsreadily without any catalyst, the amine itself being sufficiently basicto catalyze the reaction. The condensation is desirably carried out at atemperature of 25 to 30 C., and since the reaction is exothermic it isusually necessary to cool the reaction mixture to maintain the desiredtemperature range.

The hydrolysis of the condensation product may be carried out by addingthis material slowly to a slight excess of a boiling solution of aqueousalkali and maintaining the resulting mixture at the boiling point withvigorous stirring until a clear solution is formed.

The present invention will now be described by reference to thefollowing specific examples. Such examples are presented for purposes ofillustration only, and the present invention is in no way to be deemedas limited thereto.

EXAMPLE l To a solution for the preparation of an NC layer containing 10percent gelatin and a small amount of a dye was added 0.075 percent ofthe N-ethylsulfomethyl carbomate derivative ofN-pentadecyl-B-iminopropionate. The NC layer was coated at a speed of 75feet per minute. The coating was found to be very uniform and free ofrepellency spots, mottle and streakiness.

EXAMPLE II To a silver halide emulsion containing gelatin as the carriermaterial was added 0.2 percent of the N'methylsulfoethyl carbomatederivative of N-lauryl-B-iminopropionate. The emulsion was coated at aspeed of feet per minute and chilled; a 4 percent gelatin solutioncontaining 0.2 percent of the same N-dodecyl-B-aminodipropionate wascoated over this chilled EXAMPLE lll To one liter of a silver halideemulsion containing 50 grams of gelatin as the carrier material wasadded one gram of the N- methylsulfoethyl carbamate derivative ofN-lauryl-B- iminopropionate (sodium-N-lauryl-B-aminopropionate). Thisemulsion was coated at a speed of 120 feet per minute. The coating wasfound to be very uniform and free of repellency spots, mottle andstreakiness. A sample of the film was developed in a black and whitedeveloper having the following formula:

Metol grams |.5 Sodium sulfite, anhydrous do 45.0 Sodium bisulfite dol.0 Hydroquinone do 3.0 Sodium carbonate. monohydraled do 6.0 Potassiumbromide do 0.8

Water to make liter L The developed film was then fixed, washed anddried. it was free of air bells whereas an emulsion coated with saponinas the surfactant showed considerable air bells.

As may be noted from the foregoing examples, photographic compositionscomprising the compounds of interest herein, provide excellent resultswith regard to a lack of air bells, repellency spots, mottle andstreakiness.

EXAMPLE lV One mol of N-lauryl-B-aminodipropionic acid was reacted with2 mols of phosgene to form the dichloro formate derivative thereof. Theresulting product was then added simultaneously with aqueous sodiumhydride to an aqueous solution of N-methyl taurine in a manner such thatthe pH was maintained between 10 and ll. The resulting solution was thenstripped under vacuum to remove water, and the residue containing theN-methyl sulfomethyl derivative of N-lauryl-B- imino dipropionate wasfiltered.

Many modifications will be apparent to persons skilled in the art.Therefore, we do not intend to be limited in the patent granted exceptas necessitated by the appended claims.

What is claimed is:

l. A coating solution for use in coating a photographic base comprisinggelatin as the colloidal carrier material and containing as a wettingagent in an amount effective to produce wetting characteristics, acompound selected from the group consisting of the compounds having thefollowing general formulas:

wherein R is an aliphatic hydrocarbon radical having from eight to 20carbon atoms, R is selected from the group consisting of hydrogen, andalkyl radicals having from one to four carbon atoms and M is selectedfrom hydrogen, ammonium, alkali metal and organic amine cations, and xis an integer of one to five.

2. A coating solution as recited in claim 1 wherein said wetting agentis the N-methyl sulfoethyl carbamate derivative ofN-lauryl-/3-iminodipropionate.

3. A coating solution as recited in claim 1 wherein the wetting agent ispresent in an amount ranging from 0.02 percent to 0.5 percent by weightbased on the volume of the solution.

, 4. A liquid photographic gelatin silver halide emulsion containing inan amount effective to produce wetting characteristics a wetting agentselected from the group consisting of the compounds having the followinggeneral formulas;

wherein R is an aliphatic hydrocarbon radical having from eight to 20carbon atoms; M is selected from the group con sisting of hydrogen, analkali metal, ammonium and an organic amine cation; and x is an integerof one to five.

5. A photographic silver halide emulsion according to claim 8 andwherein said wetting agent is the N-methyl sulfoethyl carbamatederivative of N-laurylfi-iminodipropionate.

6. A liquid photographic silver halide emulsion as recited in claim 4wherein the amount of the wetting agent present in the emulsion is from0.02 percent to 0.5 percent by weight based on the volume of theemulsion to be coated.

7. A photographic element carrying on a suitable base a layer comprisinggelatin as the colloidal carrier material said layer containing in anamount effective to produce wetting characteristics a B-alaninederivative selected from the group consisting of those compounds havingthe following general formulas;

wherein R is an aliphatic hydrocarbon radical having from eight to 20carbon atoms; M is selected from the group consisting of hydrogen,alkali metal, ammonium and an organic amine cation; and x is an integerof one to five.

2. A coating solution as recited in claim 1 wherein said wetting agentis the N-methyl sulfoethyl carbamate derivative of N-lauryl- Beta-iminodipropionate.
 3. A coating solution as recited in claim 1 whereinthe wetting agent is present in an amount ranging from .02 percent to0.5 percent by weight based on the volume of the solution.
 4. A liquidphotographic gelatin silver halide emulsion containing in an amounteffective to produce wetting characteristics a wetting agent selectedfrom the group consisting of the compounds having the following generalformulae:
 5. A photographic silver halide emulsion according to claim 8and wherein said wetting agent is the N-methyl sulfoethyl carbamatederivative of N-lauryl- Beta -iminodipropionate.
 6. A liquidphotographic silver halide emulsion as recited in claim 4 wherein theamount of the wetting agent present in the emulsion is from .02 percentto 0.5 percent by weight based on the volume of the emulsion to becoated.
 7. A photographic element carrying on a suitable base a layercomprising gelatin as the colloidal carrier material said layercontaining in an amount effective to produce wetting characteristics aBeta -alanine derivative selected from the group consisting of thosecompounds having the following general formulae: